WO2016011613A1 - Électrolytes pour batteries au lithium-métal de transition-phosphate - Google Patents

Électrolytes pour batteries au lithium-métal de transition-phosphate Download PDF

Info

Publication number
WO2016011613A1
WO2016011613A1 PCT/CN2014/082797 CN2014082797W WO2016011613A1 WO 2016011613 A1 WO2016011613 A1 WO 2016011613A1 CN 2014082797 W CN2014082797 W CN 2014082797W WO 2016011613 A1 WO2016011613 A1 WO 2016011613A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbonate
lithium
methyl
ethyl
electrolyte composition
Prior art date
Application number
PCT/CN2014/082797
Other languages
English (en)
Inventor
Meimei WU
Xueshan Hu
Original Assignee
Basf Corporation
Basf Battery Materials (Suzhou) Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Basf Corporation, Basf Battery Materials (Suzhou) Co., Ltd. filed Critical Basf Corporation
Priority to PCT/CN2014/082797 priority Critical patent/WO2016011613A1/fr
Priority to US15/324,059 priority patent/US20170207486A1/en
Publication of WO2016011613A1 publication Critical patent/WO2016011613A1/fr

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0567—Liquid materials characterised by the additives
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0568—Liquid materials characterised by the solutes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0017—Non-aqueous electrolytes
    • H01M2300/0025—Organic electrolyte
    • H01M2300/0028—Organic electrolyte characterised by the solvent
    • H01M2300/0037—Mixture of solvents
    • H01M2300/004—Three solvents
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to non-aqueous electrolytic solutions and secondary (rechargeable) electrochemical energy storage devices comprising the same.
  • Such electrolytic solutions enhance electrochemical performance in devices charged to higher voltages, reduce capacity degradation during cycling at these voltages and during high temperature storage and in general improve the overall electrochemical stability of a device made therewith.
  • the present invention relates to rechargeable batteries that contain one or more lithium transition metal phosphate cathode active materials and contain non-aqueous electrolyte compositions comprising (a) one or more ionic salts; (b) one or more solvents; and (c) and an additive consisting of one or more C5-C7 monocycloalkane compounds and derivatives thereof.
  • Electrolytes for lithium compound containing energy storage devices are mixtures comprised of one or more highly soluble lithium salts and inorganic additives dissolved in one or more organic solvents. Electrolytes are responsible for ionic conduction between the cathode and the anode in the battery and thus essential to the operation of the system. More research and development on lithium transition metal phosphate batteries is being carried out in order to meet high energy density requirements for new application fields such as power tools, electric vehicles (EV), hybrid electric vehicles (HEV) and plug-in hybrid electric vehicles (PHEV). Further research and development on lithium transition metal phosphates (L1MPO 4 ) such as LiFeP0 4 (LFP) is being carried out in order to meet high power density requirements for these new applications.
  • L1MPO 4 lithium transition metal phosphates
  • LFP LiFeP0 4
  • An embodiment of this invention is a secondary battery comprising:
  • an electrolytic solution comprising a non-aqueous electrolytic solvent comprising (i) one or more ionic salts; (ii) one or more solvents; and (iii) an additive consisting of one or more C5-C7 monocycloalkane compounds and derivatives thereof.
  • a further embodiment involves non-aqueous electrolytic solutions suitable for use in electrochemical energy storage devices (e.g., lithium metal batteries, lithium ion batteries, lithium ion capacitors and supercapacitors) that may include salts, solvents, and may also include solid electrolyte interphase (SEI) formers, fluorinated compounds, compounds that promote high temperature stability, as well as performance enhancing additives such as overcharge protection agents, non-flammable agents, anti-swelling agent, and low temperature performance enhancers.
  • electrochemical energy storage devices e.g., lithium metal batteries, lithium ion batteries, lithium ion capacitors and supercapacitors
  • SEI solid electrolyte interphase
  • One additional embodiment provides non-aqueous electrolytic solutions that have high voltage stability during room temperature and high temperature cell cycling as well as good performance under high temperature storage conditions.
  • Figure 1 shows cycle curves of lithium-ion batteries according to examples 3, 4 and comparative example 1 up to 500 cycles.
  • Figure 3 shows cycle curves of lithium-ion batteries according to examples 1, 2 and comparative example 1 up to 500 cycles.
  • Ri,and R 2 are each independently H, Ci-Cio alkyl, halogen groups.
  • the Riand R 2 alkyl substituents are independently Ci-Cg alkyl, preferably C 1 -C4 alkyl moieties.
  • Alkyl includes linear or branched alkyl, and non-limiting examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl.
  • Non- limiting examples of branched alkyl substituent groups include -CH(CH 3 ) 2 , -CH(CH 3 )(CH 2 CH 3 ), - CH(CH 2 CH 3 ) 2 , -C(CH 3 ) 3 , -C(CH 2 CH 3 ) 3 , -CH 2 CH(CH 3 ) 2 , -CH 2 CH(CH 3 )(CH 2 CH 3 ),
  • Ri an ethyl and R 2 is hydrogen, particularly preferred is ethylcyclohexane.
  • cyclopentane cyclohexane, cycloheptane, methylcyclopentane, 1 ,3 -dimethylcyclopentane, 1 , 1 ,3 -trimethylcyclopentane,
  • ethylcyclopentane methylcyclohexane, 1,1-dimethylcyclohexane, 1,3-dimethylcyclohexane, 1 ,4-dimethylcyclohexane, ethylcyclohexane, propylcyclopentane, 1,1,3- trimethylcyclohexane, 1-t-butyl-l -methylcyclohexane, 1,2-dimethylcyclohexane, l-ethyl-3- methylcyclohexane, 1 -ethyl -4-methylcyclohexane, propylcyclohexane, 1,3-diethyl- cyclohexane, 1,4-diethyl-cyclohexane, l-methyl-3-isopropylcyclohexane, butylcyclohexane, 1, 3 -diethyl-5 -methylcyclohexane, 1 -ethy
  • the content of the cycloalkane additives isO.1-10% preferablyO.1-7%, more preferably 0.2%-5% based on the total weight of the electrolyte.
  • a further embodiment involves non-aqueous electrolytic solutions suitable for use in electrochemical energy storage devices (e.g., lithium metal batteries, lithium ion batteries, lithium ion capacitors and supercapacitors) that include salts, solvents, C 5 -C 7 monocyclohexanes (represented by formula 2) and may additionally include solid electrolyte interphase (SEI) formers, fluorinated compounds, compounds that promote high temperature stability, as well as performance enhancing additives such as overcharge protection agents, non-flammable agents, anti-swelling agent, and low temperature performance enhancers.
  • electrochemical energy storage devices e.g., lithium metal batteries, lithium ion batteries, lithium ion capacitors and supercapacitors
  • SEI solid electrolyte interphase
  • the additive can further comprise vinylene carbonate, prop- 1-ene- 1,3- sultone or combinations thereof.
  • the content of vinylene carbonate is l-5wt% based on the total weight of the electrolyte.
  • the solute of the electrolytic solution of the invention contain an ionic salt containing at least one positive ion. Typically this positive ion is lithium (Li+).
  • the salts herein function to transfer charge between the negative electrode and the positive electrode of the battery system.
  • the concentration of the lithium salt in the electrolyte is 0.5-2 mol L, preferably 0.8-1.5 mol/L.
  • the lithium salt is selected from the group consisting of lithium hexafluorophosphate (LiPF 6 ), lithium bis(oxalate)borate (LiBOB), lithium difluoro(oxalato)borate (LiODFB), lithium tetrafluoroborate (LiBF 4 ), lithium perchlorate (LiC10 ), lithium trifluoromethanesulfonate (LiCF 3 S0 3 ), bis(trifluoromethane)sulfonimide lithium (LiTFSI) and combinations thereof.
  • LiPF 6 lithium hexafluorophosphate
  • LiBOB lithium bis(oxalate)borate
  • LiODFB lithium difluoro(oxalato)borate
  • LiBF 4 lithium tetrafluoroborate
  • LiC10 lithium perchlorate
  • LiCF 3 S0 3 lithium trifluoromethanesulfonate
  • LiTFSI bis(trifluoromethane)sulfonimi
  • the lithium salt is selected from the group consisting of lithium hexafluorophosphate, lithium bis(oxalate)borate, lithium difluoro(oxalato)borate, lithium tetrafluoroborate and combination thereof.
  • concentration of the lithium salt in the electrolyte is 0.8-1.5 mol L.
  • the lithium salt is selected from the group consisting of lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF4) and combination thereof. More preferably, the lithium salt is a mixture of lithium hexafluorophosphate (LiPF 6 ) and lithium tetrafluoroborate (LiBF ), and the total concentration of both is 0.5-2 mol/L, preferably 0.8-1.5 mol/L.
  • the electrolytic solution comprises LiPF 6 as the ionic salt.
  • the amount of salt is between 5% to 20% of the total electrolyte weight, more preferably, the amount of salt is between 10% to 15% of the total electrolyte weight.
  • solvents to be used in the secondary batteries of the invention can be any of a variety of non-aqueous, aprotic, and polar organic compounds. Generally, solvents may be carbonates, carboxylates, ethers, lactones, sulfones, phosphates, nitriles, and ionic liquids.
  • Useful carbonate solvents herein include, but are not limited to: cyclic carbonates, such as propylene carbonate and butylene carbonate, and linear carbonates, such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, and ethyl propyl carbonate.
  • cyclic carbonates such as propylene carbonate and butylene carbonate
  • linear carbonates such as dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, ethyl methyl carbonate, methyl propyl carbonate, and ethyl propyl carbonate.
  • Useful carboxylate solvents include, but are not limited to: methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, and butyl butyrate.
  • Useful ethers include, but are not limited to: tetrahydrofuran, 2-methyl tetrahydrofuran, 1,3-dioxolane, 1,4- dioxane, 1,2-dimethoxyethane, 1,2-diethoxyethane, 1, 2 -dibutoxy ethane, methyl nonafluorobutyl ether, and ethyl nonafluorobutyl ether.
  • Useful lactones include, but are not limited to: ⁇ - butyrolactone, 2-methyl-y-butyrolactone, 3 -methyl - ⁇ -butyrolactone, 4- methyl-y-butyrolactone, ⁇ - propiolactone, and ⁇ -valerolactone.
  • Useful phosphates include, but are not limited to: trim ethyl phosphate, triethyl phosphate, tris(2-chloroethyl) phosphate, tris(2,2,2-trifluoroethyl) phosphate, tripropyl phosphate, triisopropyl phosphate, tributyl phosphate, trihexyl phosphate, triphenyl phosphate, tritolyl phosphate, methyl ethylene phosphate, and ethyl ethylene phosphate.
  • Useful sulfones include, but are not limited to: non-fluorinated sulfones, such as dimethyl sulfone and ethyl methyl sulfone, partially fluorinated sulfones, such as methyl trifluoromethyl sulfone, ethyl trifluoromethyl sulfone, methyl pentafluoroethyl sulfone, and ethyl pentafluoroethyl sulfone, and fully fluorinated sulfones, such as di(trifluoromethyl) sulfone, di(pentafluoroethyl) sulfone, trifluoromethyl pentafluoroethyl sulfone, trifluoromethyl nonafluorobutyl sulfone, and pentafluoroethyl nonafluorobutyl sulfone.
  • An ionic liquid (IL) is a salt in the liquid state. In some contexts, the term has been restricted to salts whose melting point is below some arbitrary temperature, such as 100 °C (212 °F). ILs are largely made of ions and short-lived ion pairs.
  • ILs Common anions of ILs are TFSi, FSi, BOB, PF 6.X R X , BF 4 , etc and cations of ILs are imidazolium, piperidinium, pyrrolidinium, tetraalkylammonium, morpholinium, etc.
  • Useful ionic liquids include, but not limited to: Bis(oxalate)borate (BOB) anion based ionic liquids, such as N-cyanoethyl-N-methylprrrolidinium BOB, 1 -methyl- 1 -(2 -methylsulfoxy)ethyl)-pyrrolidinium BOB, and l-methyl-l-((l,3,2- dioxathiolan-2-oxide-4-yl)methyl)pyrrolidinium BOB; tris(pentafluoroethyl)trifluorophosphate (FAP) anion based ionic liquids, such as N-allyl- N-methylpyrrrolidinium FAP, N-(oxiran-2- ylmethyl)N-methylpyrrolidinium FAP, and N-(prop-2-inyl)N-methylpyrrolidinium FAP; bis(trifluoromethanesulfonyl)imide (TFSI) ani
  • solvents may be used in the electrolytic solution.
  • Other solvents may be utilized as long as they are non-aqueous and aprotic, and are capable of dissolving the salts, such as ⁇ , ⁇ -dimethyl formamide, ⁇ , ⁇ -dimethyl acetamide, N,N-diethyl acetamide, and ⁇ , ⁇ -dimethyl trifluoroacetamide.
  • Carbonates are preferred, with the most preferred being ethylene carbonate (EC), ethyl methyl carbonate (EMC) and mixtures thereof.
  • the amount of solvent is between 70% to 95% of the total electrolyte weight, more preferably, the amount of salt is between 80% to 90% of the total electrolyte weight.
  • the non-aqueous solvent is selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC), methyl ethyl carbonate (EMC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ⁇ -butyrolactone (GBL), methyl propyl carbonate (MPC), methyl formate (MF), ethyl formate (EF), methyl acetate (MA), ethyl acetate (EA), ethyl propionate (EP), ethyl butyrate (EB), acetonitrile (AN), ⁇ , ⁇ -dimethyllformamide (DMF) and combination thereof.
  • EC ethylene carbonate
  • PC propylene carbonate
  • EMC dimethyl carbonate
  • DEC diethyl carbonate
  • GBL ⁇ -butyrolactone
  • MPC methyl propyl carbonate
  • MF methyl formate
  • EF ethyl formate
  • MA methyl a
  • the non-aqueous organic solvent is a mixture of two or more solvents selected from the group consisting of ethylene carbonate (EC), propylene carbonate (PC), methyl ethyl carbonate (EMC), dimethyl carbonate (DMC), and diethyl carbonate (DEC).
  • EC ethylene carbonate
  • PC propylene carbonate
  • EMC methyl ethyl carbonate
  • DMC dimethyl carbonate
  • DEC diethyl carbonate
  • the non-aqueous organic solvent comprises 5-20wt% ethylene carbonate, 20-50wt% methyl ethyl carbonate, and 20-60wt% dimethyl carbonate.
  • SEl Solid Electrolyte Interphase
  • SEl additives include vinylene carbonate(VC), vinylethylene carbonate (VEC), methylene ethylene carbonate (or 4- vinyl-l,3-dioxolan-2-one) (MEC), monofluoroethylene carbonate (FEC), Chloroethylene carbonate (CEC), 4,5-divinyl-l,3-dioxolan-2-one, 4-methyl-5 -vinyl- 1,3- dioxolan-2-one, 4-ethyl-5-vinyl-l,3-dioxolan-2-one, 4-propyl-5-vinyl-l,3-dioxolan-2-one, 4- butyl-5- vinyl-l,3-dioxolan-2-one, 4-pentyl-5-vinyl-l,3-dioxolan-2-one, 4-hexyl-5 -vinyl- 1,3- dioxolan-2-one, 4-phenyl-5-vinyl-l,3-dio
  • Particularly useful solid electrolyte interphase formers are selected from the group consisting of vinylene carbonate, monofluoroethylene carbonate, methylene ethylene carbonate, vinyl ethylene carbonate, lithium bis(oxalate)borate and mixtures thereof.
  • the amount of SEl former is between 0.1% to 8% of the total electrolyte weight, more preferably, the amount of SEl former is between 1% to 5% of the total electrolyte weight.
  • Fluorinated compounds can include organic and inorganic fluorinated compounds. Each provided in an amount of 0 to 50% by weight of the electrolyte solution.
  • Organic fluorinated compounds - Compounds in the organic family of fluorinated compounds can include fluorinated carbonates, fluorinated ethers, fluorinated esters, fluorinated alkanes, fluorinated alkyl phosphates, fluorinated aromatic phosphates, fluorinated alkyl phosphonates, and fluorinated aromatic phosphonates.
  • Exemplary organic fluorinated compounds include fluorinated alkyl phosphates, such as tris(trifluoroethyl)phosphate, tris(l,l,2,2-tetrafluoroethyl) phosphate, tris(hexafluoro- isopropyl)phosphate, (2,2,3,3- tetrafluoropropyl) dimethyl phosphate, bis(2,2,3,3- tetrafluoropropyl) methyl phosphate, and tris(2,2,3,3-tetrafluoropropyl) phosphate; fluorinated ethers, such as 3-(l,l,2,2-tetrafluoroethoxy)- (l,l,2,2-tetrafluoro)-propane, pentafluoropropyl methyl ether, pentafluoropropyl fluoromethyl ether, pentafluoropropyl trifluorom ethyl ether, 4,4,4,3
  • fluorinated esters such as (2,2,3,3-tetrafluoropropyl) formate, methyl trifluoroacetate, ethyl trifluoroacetate, propyl trifluoroacetate, trifluoromethyl trifluoroacetate, trifluoroethyl trifluoroacetate, perfluoroethyl trifluoroacetate, and (2,2,3,3- tetrafluoropropyl) trifluoroacetate; fluorinated alkanes, such as n-C 4 FgC 2 H 55 n-CgF 13 C 2 H 5 , or n- C 8 F 16 H; fluorinated aromatic phosphates, such as tris(4-fluorophenyl) phosphate and pentafluorophenyl phosphate.
  • fluorinated alkanes such as n-C 4 FgC 2 H 55 n-CgF 13 C 2 H 5 , or n- C 8 F
  • Fluorinated alkyl phosphonate such as trifluoromethyl dimethylphosphonate, trifluoromethyl di(trifluoromethyl)phosphonate, and (2,2,3,3- tetrafluoropropyl) dimethylphosphonate; fluorinated aromatic phosphonate, such as phenyl di(trifluoromethyl)phosphonate and 4 -fluorophenyl dimethylphosphonate, are suitable. Combinations of two or more of any of the foregoing are also suitable.
  • Inorganic fluorinated compounds - Compounds in the inorganic family of fluorinated compounds include lithium salts of fluorinated chelated orthoborates, fluorinated chelated orthophosphates, fluorinated imides, fluorinated sulfonates.
  • Exemplary inorganic fluorinated compounds include LiBF 2 C 2 0 4 (LiDFOB), LiPF 4 (C 2 0 4 ) (LiTFOP), LiPF 2 (C 2 0 4 ) 2 (LiDFOP), LiN(S0 2 CF 3 ) 2 (LiTFSI), LiN(S0 2 F) 2 (LiFSI), LiN(S0 2 C 2 F 5 ) 2 (LiBETI), LiCF 3 S0 3 , Li 2 B 12 FxH (12 . x) where 0 ⁇ x ⁇ 12 and combinations of two or more thereof.
  • Compounds that promote high temperature stability When batteries are operated or stored at 55 ° C or above, they tend to have poor capacity retention and swelling phenomenon due to gas generation that results from decomposition of the electrolyte at the cathode. This reduced performance becomes more evident when a cell is charged to higher voltages.
  • High temperature stabilizers can enhance charge-discharge characteristics of batteries and effectively reduce the swelling of batteries at elevated temperatures. They can also help to create a protective layer on the surface of the cathode which will further decrease the amount of solvent oxidation and decomposition at the cathode.
  • Compounds that promote high temperature stability typically include: sulfur-containing linear and heterocyclic, unsaturated and saturated compounds; phosphorus containing linear and heterocyclic, unsaturated and saturated compounds; and compounds that act as HF scavengers.
  • Sulfur containing compounds include linear and cyclic compounds such as sulfites, sulfates, sulfoxides, sulfonates, thiophenes, thiazoles, thietanes, thietes, thiolanes, thiazolidines, thiazines, sultones, and sulfones. These sulfur containing compounds can include various degrees of fluorine substitution up to and including the fully perfluorinated compunds.
  • sulfur-containing linear and cyclic compounds include ethylene sulfite, ethylene sulfate, thiophene, benzothiophene, benzo[c]thiophene, thiazole, dithiazole, isothiazole, thietane, thiete, dithietane, dithiete, thiolane, dithiolane, thiazolidine, isothiazolidine, thiadiazole, thiane, thiopyran, thiomorpholine, thiazine, dithiane, dithiine; thiepane; thiepine; thiazepine; prop-l-ene-l,3-sultone; propane-l,3-sultone; butane- 1,4-sultone; 3-hydroxy-l- phenylpropanesulfonic acid 1,3-sultone; 4-hydroxy-l-phenylbutanesulfonic acid 1,4-sultone; 4- hydroxy
  • sulfur containing compounds are selected from the group consisting propane-l,3-sultone, butane- 1,4-sultone and prop-l-ene-l,3-sultone, each provided in an amount of 0.1 to 5.0% by weight of the electrolyte solution.
  • Phosphorus containing compounds include linear and cyclic, phosphates and phosphonates.
  • Representative examples of the phosphorus containing compounds include: alkyl phosphates, such as trimethylphosphate, triethylphosphate, triisopropyl phosphate, propyl dimethyl phosphate, dipropyl methyl phosphate, and tripropyl phosphate; aromatic phosphates, such as triphenyl phosphate; alkyl phosphonates include trimethylphosphonate, and propyl dimethylphosphonate; and aromatic phosphonates, such as phenyl dimethylphosphonate. Combinations of any of the foregoing are also suitable.
  • the amount of phosphorus containing compounds is between 0.1% to 5% of the total electrolyte weight, more preferably, the amount of phosphorus containing compounds is between 1% to 4% of the total electrolyte weight.
  • Compounds that promote high temperature stability also include additives that work as a HF scavenger to prevent battery capacity deterioration and improve output characteristics at high temperatures, including acetamides, anhydrides, Pyridines, tris(trialkylsilyl)phosphates, tris(trialkylsilyl)phosphites, tris(trialkylsilyl)borates.
  • HF scavenger-type high temperature stabilizers include: acetamides such as, N,N-dimethyl acetamide, and 2,2,2-trifluoroacetamide; anhydrides such as phthalic anhydride succinic anhydride, and glutaric anhydride; pyridines such as antipyridine and pyridine; tris(trialkylsilyl)phosphates such as tris(trimethylsilyl)phosphate and tris(triethylsilyl)phosphate; tris(trialkylsilyl)phosphites tris(trimethylsilyl)phosphite, tris(triethylsilyl)phosphite, tris(tripropylsilyl)phosphit; tris(trialkylsilyl)borates such as, tris(trimethylsilyl)borate, tris(triethylsilyl)borate, and tris(tripropylsilyl)borate;
  • An embodiment of this invention includes a secondary electrochemical energy storage device electrolyte which comprises:
  • an additive consisting of one or more C 5 -C 7 monocycloalkane compounds and derivatives thereof.
  • the anode material is selected from lithium metal, lithium alloys, carbonaceous materials, and lithium metal oxides capable of being intercalated and de- intercalated with lithium ions.
  • Carbonaceous materials useful herein include graphite, amorphous carbon, and other carbon materials such as activated carbon, carbon fiber, carbon black, and mesocarbon microbeads.
  • Lithium metal anodes may be used. Lithium MMOs (mixed-metal oxides) such as LiMn0 2 and Li 4 Ti 5 0 12 are also envisioned.
  • Alloys of lithium with transition or other metals may be used, including LiAl, LiZn, Li 3 Bi, Li 3 Cd, Li 3 Sb, Li 4 Si, Li 4 4 Pb, Li 4 4 Sn, LiC 6 , Li 3 FeN 2 , Li 2 6 Co 0 4 N, Li 2 6 Cu 04 N, and combinations thereof.
  • the anode may further comprise an additional material such as a metal oxide including SnO, Sn0 2 , GeO, Ge0 2 , ln 2 0, ln 2 0 3 , PbO, Pb0 2 , Pb 2 0 3 , Pb 3 04, Ag 2 0, AgO, Ag 2 0 3 , Sb 2 0 3 , Sb 2 0 4 , Sb 2 0 5 , SiO, ZnO, CoO, NiO, FeO, and combinations thereof. Silicon may also be used.
  • a metal oxide including SnO, Sn0 2 , GeO, Ge0 2 , ln 2 0, ln 2 0 3 , PbO, Pb0 2 , Pb 2 0 3 , Pb 3 04, Ag 2 0, AgO, Ag 2 0 3 , Sb 2 0 3 , Sb 2 0 4 , Sb 2 0 5 , SiO, ZnO, CoO, NiO, FeO, and combinations thereof.
  • the cathode comprises at least one, lithium transition metal phosphate (LiMP0 4 ) Lithium transition metal phosphate (LiMP0 4 ) such as LiFeP0 4 , LiVP0 4 , LiMnP0 4 , LiCoP0 4 , LiNiP0 4 , LiMn x Mc y P0 4 , where Mc may be one of or of Fe, V, Ni, Co, Al, Mg, Ti, B, Ga, or Si and 0 ⁇ x,y ⁇ l .
  • LiMP0 4 Lithium transition metal phosphate
  • LiMP0 4 Lithium transition metal phosphate
  • Mc may be one of or of Fe, V, Ni, Co, Al, Mg, Ti, B, Ga, or Si and 0 ⁇ x,y ⁇ l .
  • transition metal oxides such as Mn0 2 and V 2 0 5
  • transition metal sulfides such as FeS 2 , MoS 2 , and TiS 2
  • conducting polymers such as polyaniline and polypyrrole
  • the preferred positive electrode materials are LiFeP0 4 and LiMnP0 4 .
  • the active cathode material is LiFeP0 4.
  • Either the anode or the cathode, or both, may further comprise a polymeric binder.
  • the binder may be polyvinylidene fluoride, styrene- butadiene rubber, alkali metal salts of carboxymethyl cellulose, alkali metal salts of polyacrylic acid, polyamide or melamine resin, or combinations of two or more thereof.
  • Further additions to the electrolytic solution may include, but are not limited to, one or more of the following performance enhancing additives: overcharge protection agent, non-flammable agents, anti-swelling agent, low temperature performance enhancers.
  • performance enhancing additives include biphenyl, iso-propyl benzene, hexafluorobenzene, phosphazenes, organic phosphates, organic phosphonates, and alkyl and aryl siloxanes, The total concentration of such additives in the solution preferably does not exceed about 5 wt%.
  • the separator placed between the cathode and the anode which allows for the transfer of ions through the electrolyte solution between the cathode and anode is selected from the group consisting of polyethylene film, polypropylene film and combinations thereof.
  • Numerical ranges of ingredients that are bounded by zero on the lower end are intended to provide support for the concept "up to [the upper limit]," for example “up to 10 vol% VC,” vice versa, as well as a positive recitation that the ingredient in question is present in an amount that does not exceed the upper limit.
  • An example of the latter is “comprises VC, provided the amount does not exceed 10 vol%.”
  • a recitation such as "8-25 vol% (EC + MEC + VC)" means that any or all of EC, MEC and/or VC may be present in an amount of 8-25 vol% of the composition. Examples of the invention
  • the electrolyte solution is prepared in BRAU glove box with argon gas of 99.999% purity and water content of ⁇ 5ppm at room temperature, wherein 12.73g ethylene carbonate, 40.73g ethyl methyl carbonate, 31.40g dimethyl carbonate, 2g vinylene carbonate and 0.5g cyclohexane are mixed evenly, and then LiPF 6 is added and mixed sufficiently to obtain l .Omol/L of LiPF 6 solution.
  • example 2 The procedure of example 2 is the same as example 1, except that 12.45g ethylene carbonate, 40.10g ethyl methyl carbonate, 30.91g dimethyl carbonate, 2g vinylene carbonate and 2g cyclohexane are mixed evenly, and then LiPF 6 is added and mixed sufficiently to obtain l.Omol/L of LiPF 6 solution.
  • Example 3 The procedure of example 3 is the same as example 1, except that 12.73g ethylene carbonate, 40.73g ethyl methyl carbonate, 31.40g dimethyl carbonate, 2g vinylene carbonate and 0.5g ethylcyclohexane are mixed evenly, and then LiPF 6 is added and mixed sufficiently to obtain l .Omol/L of LiPF 6 solution.
  • Example 4 The procedure of example 4 is the same as example 1, except that 12.45g ethylene carbonate, 40.10g ethyl methyl carbonate, 30.91g dimethyl carbonate, 2g vinylene carbonate and 2g ethylcyclohexane are mixed evenly, and then LiPF 6 is added and mixed sufficiently to obtain l .Omol/L of LiPF 6 solution.
  • Example 5 The procedure of example 5 is same as example 1, except that 12.40g ethylene carbonate, 39.68g ethyl methyl carbonate, 30.59g dimethyl carbonate, 2g vinylene carbonate, 3g ethylcyclohexane are mixed evenly, and then LiPF 6 is added and mixed sufficiently to obtain l .Omol/L of LiPF 6 solution.
  • example 6 The procedure of example 6 is the same as example 1, except that 12.14g ethylene carbonate, 38.85g ethyl methyl carbonate, 29.95g dimethyl carbonate, 2g vinylene carbonate and 5g ethylcyclohexane are mixed evenly, and then LiPF 6 is added and mixed sufficiently to obtain l .Omol/L of LiPF 6 solution.
  • the electrolyte solution is prepared in BRAUN glove box with argon gas of 99.999% purity and water content of ⁇ 5ppm at room temperature, wherein 12.79g ethylene carbonate, 40.94g ethyl methyl carbonate, 31.56g dimethyl carbonate and 2g vinylene carbonate are mixed evenly, and then LiPF 6 is added and mixed sufficiently to obtain l.Omol/L of LiPF 6 solution. Test and results
  • the dry cell comprises LiFeP0 4 as cathode and AG (Artificial Graphite) as anode and purchased from TianJin BAK Battery CO., LTD and the design capacity of the lithium ion battery is lOOOmAh. Dry cell is placed in the oven of 85°C for 24 hours and then transferred to glove box for use. The electrolyte solutions prepared according to examples and comparative examples are injected into dried cell, then sealing and remained for 24 hours, and formation, to obtain the lithium ion batteries.
  • the lithium ion batteries are measured at 60°C / 1C cycle with cut-off voltage range
  • Figure 1 shows the comparison of cycling performances of LFP batteries at 60°C, and it indicates that the cycle capacity retention of the present LFP batteries is more than 79% after 400 cycles, while the cycle capacity retention of comparison example is less than 70% after 400 cycles.
  • the lithium ion batteries are measured at RT(25°C) / 1C cycle with cut-off voltage range 2.0V-3.65V by using capacity test cabinet for lithium ion batteries (NEWARE CT-3008W- 5V-6A). The results are shown in figures 2.
  • Figure 2 shows the comparison of cycling performances of LFP batteries at RT, and it indicates that the cycle capacity retention of the present LFP batteries is more than 84% after 1500 cycles, while the cycle capacity retention of comparison example is less than 77% after 1500 cycles.
  • Figure 3 shows the comparison of cycling performances of LFP batteries at 60°C, and it indicates that the cycle capacity retention of the present LFP batteries is better than the cycle capacity retention of comparison example after 400 cycles.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Secondary Cells (AREA)

Abstract

L'invention concerne des solutions électrolytiques et des batteries rechargeables les contenant. Les solutions électrolytiques contiennent un additif constitué d'un ou de plusieurs composés de monocycloalkane en C 5 à C 7 et des dérivés de ceux-ci.
PCT/CN2014/082797 2014-07-23 2014-07-23 Électrolytes pour batteries au lithium-métal de transition-phosphate WO2016011613A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/CN2014/082797 WO2016011613A1 (fr) 2014-07-23 2014-07-23 Électrolytes pour batteries au lithium-métal de transition-phosphate
US15/324,059 US20170207486A1 (en) 2014-07-23 2014-07-23 Electrolytes for lithium transition metal phosphate batteries

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/CN2014/082797 WO2016011613A1 (fr) 2014-07-23 2014-07-23 Électrolytes pour batteries au lithium-métal de transition-phosphate

Publications (1)

Publication Number Publication Date
WO2016011613A1 true WO2016011613A1 (fr) 2016-01-28

Family

ID=55162416

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2014/082797 WO2016011613A1 (fr) 2014-07-23 2014-07-23 Électrolytes pour batteries au lithium-métal de transition-phosphate

Country Status (2)

Country Link
US (1) US20170207486A1 (fr)
WO (1) WO2016011613A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106532117A (zh) * 2016-11-17 2017-03-22 张家港市国泰华荣化工新材料有限公司 一种锂离子电池电解液及锂离子电池

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109476688B (zh) 2016-04-01 2022-03-11 诺姆斯技术公司 包含磷的改性离子液体
US10707531B1 (en) 2016-09-27 2020-07-07 New Dominion Enterprises Inc. All-inorganic solvents for electrolytes
KR102638417B1 (ko) 2017-07-17 2024-02-19 놈스 테크놀로지스, 인크. 인 함유 전해질
KR102138128B1 (ko) * 2018-11-26 2020-07-27 동우 화인켐 주식회사 전해액 조성물 및 이를 이용한 이차전지
CN114583263B (zh) * 2020-11-30 2023-11-14 比亚迪股份有限公司 电解液、正极、锂离子电池和车辆
WO2022116170A1 (fr) * 2020-12-04 2022-06-09 宁德新能源科技有限公司 Électrolyte, et dispositif électrochimique et dispositif électronique comprenant un électrolyte
CN112490502B (zh) * 2020-12-04 2022-01-21 广州天赐高新材料股份有限公司 一种电解液及锂二次电池
CN114639870B (zh) * 2020-12-15 2023-05-26 张家港市国泰华荣化工新材料有限公司 一种锂离子电池的电解液及锂离子电池
KR20230134521A (ko) * 2021-01-22 2023-09-21 글로벌 그래핀 그룹, 인크. 난연성 준-고체 및 고체 상태 전해질, 리튬 전지 및제조 방법
US11949109B2 (en) * 2021-03-12 2024-04-02 Honeycomb Battery Company Flame-resistant electrodes lithium containing quasi-solid or solid-state electrolytes and manufacturing method
US11881580B2 (en) * 2021-03-19 2024-01-23 Global Graphene Group, Inc. Flame-resistant bipolar electrodes, bipolar lithium batteries, and manufacturing method
US11888119B2 (en) * 2021-04-07 2024-01-30 Global Graphene Group, Inc. Method of producing flame-resistant quasi-solid electrolytes and lithium batteries containing same

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1176658A2 (fr) * 2000-07-25 2002-01-30 Samsung SDI Co. Ltd. Electrolyte pour batterie du type lithium-soufre et batterie de ce type comportant cet électrolyte
US20030129498A1 (en) * 2001-12-28 2003-07-10 Quallion, Llc Electrolyte system and energy storage device using same
US20070003838A1 (en) * 2004-09-22 2007-01-04 Yoshiaki Kumashiro Energy device
CN101916878A (zh) * 2010-08-27 2010-12-15 上海奥威科技开发有限公司 一种以γ-丁内酯为基础溶剂的低温有机电解液及其应用
US20120130135A1 (en) * 2010-11-16 2012-05-24 Takashi Takeuchi Nonaqueous solvent for electrical storage device
US20120321964A1 (en) * 2011-06-15 2012-12-20 Masaki Hasegawa Nonaqueous solvent and nonaqueous electrolytic solution for electrical storage device and nonaqueous electrical storage device, lithium secondary battery and electric double layer capacitor using the same

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009176719A (ja) * 2007-12-26 2009-08-06 Sony Corp 電解液、二次電池およびスルホン化合物
EP2352157B1 (fr) * 2008-10-21 2014-04-16 Panasonic Corporation Solvant non aqueux et solution électrolytique non aqueuse pour dispositif de stockage d'énergie, et dispositif de stockage d'énergie les utilisant, tel que batterie rechargeable au lithium ou condensateur électrique à double couche
KR101412899B1 (ko) * 2010-02-12 2014-06-26 미쓰비시 가가꾸 가부시키가이샤 비수계 전해액 및 비수계 전해액 2 차 전지
KR101837036B1 (ko) * 2011-03-30 2018-03-09 삼성전자주식회사 리튬 이차 전지용 전해질 및 이를 채용한 리튬 전지
JP2013171683A (ja) * 2012-02-20 2013-09-02 Panasonic Corp 蓄電デバイス
JP5810014B2 (ja) * 2012-03-15 2015-11-11 富士フイルム株式会社 非水二次電池用電解液及び二次電池

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1176658A2 (fr) * 2000-07-25 2002-01-30 Samsung SDI Co. Ltd. Electrolyte pour batterie du type lithium-soufre et batterie de ce type comportant cet électrolyte
US20030129498A1 (en) * 2001-12-28 2003-07-10 Quallion, Llc Electrolyte system and energy storage device using same
US20070003838A1 (en) * 2004-09-22 2007-01-04 Yoshiaki Kumashiro Energy device
CN101916878A (zh) * 2010-08-27 2010-12-15 上海奥威科技开发有限公司 一种以γ-丁内酯为基础溶剂的低温有机电解液及其应用
US20120130135A1 (en) * 2010-11-16 2012-05-24 Takashi Takeuchi Nonaqueous solvent for electrical storage device
US20120321964A1 (en) * 2011-06-15 2012-12-20 Masaki Hasegawa Nonaqueous solvent and nonaqueous electrolytic solution for electrical storage device and nonaqueous electrical storage device, lithium secondary battery and electric double layer capacitor using the same

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106532117A (zh) * 2016-11-17 2017-03-22 张家港市国泰华荣化工新材料有限公司 一种锂离子电池电解液及锂离子电池

Also Published As

Publication number Publication date
US20170207486A1 (en) 2017-07-20

Similar Documents

Publication Publication Date Title
KR102298774B1 (ko) 리튬 이온 배터리를 위한 4.2 v 이상의 캐소드 재료와 함께 사용하기 위한 비수성 전해질 용액에서의 리튬 비스(플루오로술포닐)이미드 (lifsi)의 용도
EP2917957B1 (fr) Solutions électrolytiques non aqueuses et cellules électrochimiques les comprenant
US20170207486A1 (en) Electrolytes for lithium transition metal phosphate batteries
KR20180061322A (ko) 고 에너지 리튬-이온 전지용 비수성 전해질
CN108028417B (zh) 含有异氰化物的锂离子电池无水电解质
CN110783626B (zh) 电解液、锂离子电池、电池模块、电池包及装置
CN110828893B (zh) 一种锂离子电池电解液及锂离子电池
KR102023678B1 (ko) 이차전지용 전해액 및 이를 포함하는 이차전지
CN109716578B (zh) 包含双官能膦酸甲硅烷基酯的电化学电池
JP6991471B2 (ja) 高電圧電池用の電解質成分としてのピリジン三酸化硫黄錯体
CN110911748B (zh) 一种锂二次电池电解液和锂二次电池
KR20190080040A (ko) 이차전지용 비수성 전해액 및 이를 포함하는 이차전지
KR102637861B1 (ko) 리튬 배터리용 전해질 조성물을 위한 헤테로환형 설폰일 플루오라이드 첨가제
CN113429433B (zh) 锂离子电池电解液和锂离子电池
CN111584930B (zh) 一种锂离子电池电解液及锂离子电池
WO2022168755A1 (fr) Solution d'électrolyte non aqueux, batterie à électrolyte non aqueux et composé
KR20190080041A (ko) 이차전지용 비수성 전해액 및 이를 포함하는 이차전지
KR102177033B1 (ko) 리튬이온 이차전지용 비수성 전해액 및 이를 포함하는 리튬이온 이차전지
WO2023054128A1 (fr) Solution électrolytique non aqueuse, batterie à électrolyte non aqueux, composé et additif pour électrolyte non aqueux
KR20240062915A (ko) 전해액 첨가제, 이를 포함하는 전지용 전해액 및 이를 포함하는 이차전지
KR20240049064A (ko) 전해액 첨가제, 이를 포함하는 전지용 전해액 및 이를 포함하는 이차전지
CN115939509A (zh) 一种电解液和锂离子电池
KR20220021414A (ko) 전해액 및 이를 포함하는 이차전지
CN115995608A (zh) 电解液、锂二次电池和提高4.55v高电压钴酸锂正极电池体系性能的方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14898243

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 15324059

Country of ref document: US

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14898243

Country of ref document: EP

Kind code of ref document: A1